Alternating sequence structure polymer-based carbon microspheres as well as preparation method and application thereof

Abstract

The invention relates to an alternating sequence structure polymer-based carbon microsphere as well as a preparation method and application thereof, and belongs to the technical field of energy storage materials. The invention relates to a polymer-based carbon microsphere with an alternating sequence structure, which is prepared by taking a synthesized polymer microsphere with an alternating sequence structure as a carbon precursor through a programmed carbonization / activation method. The controllable preparation of the alternating polymer microspheres is realized by selecting proper reaction monomers, changing and regulating the structure of a polymer precursor and optimizing a pyrolysis process. The prepared carbon microspheres are composed of C, N and O, the particle size is uniform and adjustable, the surface is smooth, the dispersity is good, and the specific surface area ranges from 2100 m < 2 >. G <-1 > to 3200 m < 2 >. G <-1 >. According to different batches of cross-carbon microspheres, the mass specific capacitance is stabilized between 260 F. G <-1 > and 420 F. G <-1 > when the current density is 1-10 A. G <-1 >, and when the current density is 10 A. G <-1 >, the capacitance retention rate is stabilized between 95% and 100% after 10000 times of charging and discharging.

Description

Technical Field

[0001] The present invention relates to the technical field of energy storage materials, and in particular to an alternating sequence structure polymer-based carbon microsphere and a preparation method and application thereof. Background Art

[0002] As a key material in the industrial foundation, carbon materials are widely used in the machinery industry, electronic appliances, aerospace and nuclear energy industries, etc., playing a huge role in industrial production and people's daily life. Carbon microspheres are an important branch of carbon materials. Because of their low density, good conductivity, large specific surface area and high thermal stability, they have become one of the key electrode materials in the field of supercapacitors.

[0003] The synthesis process of carbon microspheres includes three steps: preparation of precursors, synthesis and pyrolysis of microspheres, and carbonization activation. Among them, the type of precursor directly affects the structure, function and application of carbon microspheres. Common polymer precursors are homopolymers and condensation polymers. Their polymer chains are usually composed of self-polymerization or binary copolymerization of a single structural unit. Compared with single-structure polymer chains, binary copolymer chains have the characteristics of rich monomer selection and diverse structural composition. The resulting carbon microspheres have uniform particle size distribution, higher thermal stability and structural controllability. However, the structure of binary copolymer chains is mostly random sequence. Even under the same experimental conditions, it is difficult to ensure the consistency of the obtained polymer chain sequence, which directly affects the structural uniformity and batch stability of carbon microspheres, and restricts the process optimization and application development of copolymer carbon microspheres. Therefore, the preparation of polymer precursors with alternating sequence structures is crucial to improving the structural uniformity and performance stability of carbon microspheres. Summary of the invention

[0004] The present invention aims to solve the technical problems of disordered structure and poor batch stability of binary copolymer carbon microspheres in the prior art, and provides an alternating sequence structure polymer-based carbon microsphere and its preparation method and application. The polymer-based carbon microspheres of the present invention have controllable and uniform size, good batch stability, large specific surface area, and excellent electrochemical performance.

[0005] In order to solve the above technical problems, the technical solutions of the present invention are as follows:

[0006] An alternating sequence structure polymer-based carbon microsphere, which is prepared by using the alternating sequence structure polymer microsphere as a carbon precursor through pyrolysis and carbonization activation steps;

[0007] The alternating sequence structure polymer microspheres are polymer microspheres with an alternating polymer chain structure formed by using a charge transfer complex formed by an electron-rich olefin and an electron-deficient olefin as a polymerization monomer through free radical polymerization.

[0008] In the above technical solution, preferably, the electron-rich olefin is a styrene monomer, or a styrene monomer substituted with a hydroxyl, amino, alkyl, alkoxy, aryloxy, boric acid or amide group.

[0009] In the above technical scheme, it is further preferred that the electron-rich olefin is styrene, p-hydroxystyrene, 4-vinylaniline, 2-aminostyrene, 4-vinylbenzeneboric acid, 4-vinylbenzenesulfonamide, 3-methoxystyrene, 4-methoxystyrene, 2,4-dimethoxy-1-vinylbenzene, p-phenoxystyrene, o-methylstyrene, 3-methoxystyrene, 4-methylstyrene, α-methylstyrene, 4-isopropylstyrene, 4-cyclohexylstyrene, 4-tert-butylstyrene, 1-ethyl-4-vinylbenzene, 1-cyclopropyl-4-vinylbenzene or 1-cyclopentyl-4-vinylbenzene.

[0010] In the above technical scheme, preferably, the electron-deficient olefin is a maleimide monomer, or a maleimide monomer substituted with a halogen atom, an amino group, a hydroxyl group, an amide group, a carboxyl group, an aromatic group or an alkyl group N, or 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene.

[0011] In the above technical scheme, it is further preferred that the electron-deficient olefin is maleimide, N-methylmaleimide, N-bromomaleimide, N-aminomaleimide, N-phenylmaleimide, N-benzylmaleimide, p-nitrobenzenemaleimide, N-carbamylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-(1-pyrene)-maleimide, 4-maleimidophenol, N-hydroxymaleimide, 2-maleimidoacetic acid, 3-maleimidopropionic acid, 4-maleimidophenol, The invention can be substituted with 1,2-dimaleimidobutyric acid, 5-maleimidopentanoic acid, 6-maleimidohexanoic acid, 4-maleimidobenzoic acid, N,N'-1,4-phenylenedimaleimide, N-hydroxyethylmaleimide, 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 9-maleimidoacridine, 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione, 1,2-dimaleimidoethane, 1,4-bis(maleimido)butane, 1,6-dimaleimidohexane or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene.

[0012] In the above technical solution, it is preferred that the alternating sequence structure polymer-based carbon microspheres are composed of C, N and O in a weight ratio of 70-90:6.1-19.5:3.9-10.5, and the carbon microspheres have uniform particle size, smooth surface and good dispersibility, and a specific surface area of ​​2100-3200m 2 ·g -1 between.

[0013] A method for preparing alternating sequence structure polymer-based carbon microspheres comprises the following steps:

[0014] A. Preparation of Charge Transfer Complex Solution

[0015] The electron-rich olefin and the electron-deficient olefin are dissolved in a mixed solution with a concentration of 60 to 80% by weight, and stirred for reaction at a temperature of 20 to 70° C. for 3 to 24 hours to obtain a charge transfer complex solution;

[0016] B. Preparation of polymerization reaction solution

[0017] Adding a crosslinking agent, an initiator and a dispersant to the charge transfer complex solution obtained in step A, and performing ultrasonic dispersion to obtain a polymerization reaction solution;

[0018] C. Preparation of polymer microspheres with alternating sequence structure

[0019] The polymerization reaction liquid obtained in step B is transferred to a three-necked flask, and the polymerization reaction is carried out at a temperature of 70-80° C. and a stirring speed of 170-300 rpm for 4-6 hours. Finally, the reactant is cooled to room temperature, the product is centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 50-70° C. for 4-6 hours to obtain alternating sequence structure polymer microspheres;

[0020] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0021] The alternating sequence structure polymer microspheres obtained in step C are placed in a tubular furnace for pre-oxidation, dry air is introduced, and the mixture is heated to 250-300°C at a heating rate of 1.0-3.0°C / min, and kept warm for 1.0-2.0h; then, the pre-oxidized product is carbonized, argon is introduced for protection, and the mixture is heated to 600-700°C at a heating rate of 2.0-3.0°C / min, and kept warm for 2.0-2.5h, and naturally cooled to room temperature to obtain a black solid; the obtained black product is mixed with KOH in a mass ratio of 1:1-5, and then heated to a temperature of 600-1000°C at a heating rate of 1.0-5.0°C / min under argon protection, and activated at this temperature for 1.0-4.0 hours, and finally naturally cooled to room temperature, and washed with deionized water until neutral, to obtain the alternating sequence structure polymer-based carbon microspheres.

[0022] In the above technical solution, it is preferred that:

[0023] In step A, the weight ratio of the electron-rich olefin, the electron-deficient olefin and the mixed solution is 0.01-0.12:0.01-0.12:1;

[0024] In step B, the weight ratio of the crosslinking agent, initiator, dispersant and mixed solution is 0.001-0.008:0.005-0.05:0.002-0.02:1.

[0025] In the above technical solution, it is preferred that:

[0026] In step A, the mixed solution is selected from a mixed solution of any two of methanol, ethanol, propanol, butanol, isopropanol, n-butanol, n-pentanol, isoamyl alcohol, acetone, ethyl acetate, isoamyl acetate, n-hexane, cyclohexane, m-xylene, and p-xylene;

[0027] In step B:

[0028] The crosslinking agent is allyl methacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, triallyl isocyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate or vinyl trimethoxysilane;

[0029] The initiator is azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide or azobiscyclohexylcarbonitrile;

[0030] The dispersant is polyvinyl pyrrolidone with an average molecular weight of 8000-1300000, polyacrylamide with a number average molecular weight (Mn) of 5000-18000000, polyacrylic acid with a weight average molecular weight (Mw) of 2000-5000 or 240000-250000, or polyvinyl alcohol with a weight average molecular weight (Mw) of 110000-130000 or 180000-200000.

[0031] Application of alternating sequence structure polymer-based carbon microspheres as negative electrode materials for all-solid-state supercapacitors.

[0032] The beneficial effects of the present invention are:

[0033] The alternating sequence structure polymer-based carbon microspheres of the present invention are prepared by a programmed carbonization / activation method using synthesized alternating sequence polymer microspheres as carbon precursors. The present invention achieves controllable preparation of alternating sequence structure polymer-based carbon microspheres by selecting suitable reaction monomers, changing and regulating the structure of polymer precursors, and optimizing the pyrolysis process. The alternating sequence structure polymer-based carbon microspheres prepared by the present invention are composed of C, N and O in a weight ratio of 70 to 90: 6.1 to 19.5: 3.9 to 10.5. The carbon microspheres have uniform and adjustable particle sizes, smooth surfaces and good dispersibility, and a specific surface area of ​​2100 to 3200 m 2 ·g -1 Different batches of alternating sequence structure polymer-based carbon microspheres have a mass specific capacitance at a current density of 1 to 10 A·g -1 Stable at 260~420F·g -1 When the current density is 10A·g -1 When the battery is charged and discharged for 10,000 times, the capacitance retention rate is stabilized at 95-100%. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0035] Figure 1 is a scanning electron microscope image of the alternating polymer microspheres prepared in Example 1;

[0036] Figure 2 is a scanning electron microscope image of the alternating sequence structure polymer-based carbon microspheres prepared in Example 1;

[0037] Figure 3 is a scanning electron microscope image of the alternating polymer microspheres prepared in Example 2;

[0038] Figure 4 is a scanning electron microscope image of the alternating sequence structure polymer-based carbon microspheres prepared in Example 2;

[0039] Figure 5 is a scanning electron microscope image of the alternating polymer microspheres prepared in Example 3;

[0040] Figure 6 is a scanning electron microscope image of the alternating sequence structure polymer-based carbon microspheres prepared in Example 3;

[0041] Figure 7 These are electrochemical performance characterization diagrams of the alternating sequence structure polymer-based carbon microspheres prepared in Example 1, wherein Figure a is a constant current charge and discharge diagram, Figure b is a cyclic voltammogram, and Figure c is a cycle stability diagram.

[0042] Figure 8These are electrochemical performance characterization diagrams of the alternating sequence structure polymer-based carbon microspheres prepared in Example 2, wherein Figure a is a constant current charge-discharge diagram, Figure b is a cyclic voltammogram, and Figure c is a cycle stability diagram. DETAILED DESCRIPTION

[0043] The present invention provides an alternating sequence structure polymer-based carbon microsphere, which is an alternating sequence structure polymer-based carbon microsphere prepared by using alternating sequence structure polymer microspheres as carbon precursors through pyrolysis and carbonization activation steps; wherein the alternating sequence structure polymer microspheres are polymerized monomers using charge transfer complexes formed by electron-rich olefins and electron-deficient olefins, and are formed by free radical polymerization to have a polymer chain structure with alternating arrangement.

[0044] Preferably, the electron-rich olefin is a styrene monomer, or a styrene monomer substituted with a hydroxyl, amino, alkyl, alkoxy, aryloxy, boric acid or amide group. Further preferably, the electron-rich olefin is styrene, p-hydroxystyrene, 4-vinylaniline, 2-aminostyrene, 4-vinylbenzene boronic acid, 4-vinylbenzene sulfonamide, 3-methoxystyrene, 4-methoxystyrene, 2,4-dimethoxy-1-vinylbenzene, p-phenoxystyrene, o-methylstyrene, 3-methoxystyrene, 4-methylstyrene, α-methylstyrene, 4-isopropylstyrene, 4-cyclohexylstyrene, 4-tert-butylstyrene, 1-ethyl-4-vinylbenzene, 1-cyclopropyl-4-vinylbenzene or 1-cyclopentyl-4-vinylbenzene.

[0045] Preferably, the electron-deficient olefin is a maleimide monomer, or a maleimide monomer substituted with a halogen atom, an amino group, a hydroxyl group, an amide group, a carboxyl group, an aromatic group or an alkyl group N, or 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene. It is further preferred that the electron-deficient olefin is maleimide, N-methylmaleimide, N-bromomaleimide, N-aminomaleimide, N-phenylmaleimide, N-benzylmaleimide, p-nitrobenzenemaleimide, N-carbamylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-(1-pyrene)-maleimide, 4-maleimidophenol, N-hydroxymaleimide, 2-maleimidoacetic acid, 3-maleimidopropionic acid, 4-maleimide butyric acid, 5-maleimidovaleric acid, 6-maleimidocaproic acid, 4-maleimidobenzoic acid, N,N'-1,4-phenylenedimaleimide, N-hydroxyethylmaleimide, 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 9-maleimidoacridine, 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione, 1,2-bismaleimidoethane, 1,4-bis(maleimido)butane, 1,6-bismaleimidohexane or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene.

[0046] Preferably, the alternating sequence structure polymer-based carbon microspheres are composed of C, N and O in a weight ratio of 70-90:6.1-19.5:3.9-10.5, and the carbon microspheres have uniform particle size, smooth surface and good dispersibility, and a specific surface area of ​​2100-3200m 2 ·g -1 between.

[0047] The alternating sequence structure polymer-based carbon microspheres of the present invention control the microsphere yield, particle size and surface morphology by regulating the amounts of electron-rich olefins and electron-deficient olefins and regulating the types and proportions of the mixed solution; regulating the amount of the crosslinking agent to increase the crosslinking degree of the product; regulating the amount of the initiator to increase the yield; and regulating the amount of the dispersant to regulate the monodispersity of the product.

[0048] The present invention provides a method for preparing alternating sequence structure polymer-based carbon microspheres, comprising the following steps:

[0049] A. Preparation of Charge Transfer Complex Solution

[0050] The electron-rich olefin and the electron-deficient olefin are dissolved in a mixed solution with a concentration of 60 to 80% by weight, and stirred for reaction at a temperature of 20 to 70° C. for 3 to 24 hours to obtain a charge transfer complex solution;

[0051] The weight ratio of the electron-rich olefin, the electron-deficient olefin and the mixed solution is 0.01-0.12:0.01-0.12:1;

[0052] In this step, the electron-rich olefin plays the role of donating electrons in the preparation of polymer microspheres and forms a charge transfer complex with the electron-deficient olefin.

[0053] The electron-rich olefin is preferably styrene, p-hydroxystyrene, 4-vinylaniline, 2-aminostyrene, 4-vinylbenzene boronic acid, 4-vinylbenzene sulfonamide, 3-methoxystyrene, 4-methoxystyrene, 2,4-dimethoxy-1-vinylbenzene, p-phenoxystyrene, o-methylstyrene, 3-methoxystyrene, 4-methylstyrene, α-methylstyrene, 4-isopropylstyrene, 4-cyclohexylstyrene, 4-tert-butylstyrene, 1-ethyl-4-vinylbenzene, 1-cyclopropyl-4-vinylbenzene or 1-cyclopentyl-4-vinylbenzene. The source of the electron-rich olefin monomer used in the present invention is not particularly limited, and it is prepared by conventional preparation methods well known to those skilled in the art or is a product currently sold on the market, such as 4-methylstyrene sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name of 4-methylstyrene.

[0054] In this step, the electron-deficient olefin plays the role of accepting electrons and forming a charge transfer complex with the electron-rich olefin in the preparation of polymer microspheres.

[0055] The electron-deficient olefin is preferably maleimide, N-methylmaleimide, N-bromomaleimide, N-aminomaleimide, N-phenylmaleimide, N-benzylmaleimide, p-nitrobenzenemaleimide, N-carbamoylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-(1-pyrene)-maleimide, 4-maleimidophenol, N-hydroxymaleimide, 2-maleimidoacetic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 5-Maleimidopentanoic acid, 6-Maleimidohexanoic acid, 4-Maleimidobenzoic acid, N,N'-1,4-phenylene dimaleimide, N-hydroxyethylmaleimide, 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 9-Maleimidoacridine, 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione, 1,2-bismaleimidoethane, 1,4-bis(maleimido)butane, 1,6-bismaleimidohexane or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene. The source of the electron-deficient olefin monomer used in the present invention is not particularly limited, and can be prepared by conventional preparation methods well known to those skilled in the art or can be products currently sold on the market, such as N-phenylmaleimide sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name N-phenylmaleimide.

[0056] In this step, the mixed solution plays the role of dissolving the electron-rich olefin and the electron-deficient olefin in the preparation of the polymer microspheres and allowing them to react smoothly, thereby regulating the morphology and structure of the microspheres.

[0057] The mixed solution is selected from any two of methanol, ethanol, propanol, butanol, isopropanol, n-butanol, n-pentanol, isoamyl alcohol, acetone, ethyl acetate, isoamyl acetate, n-hexane, cyclohexane, m-xylene, and p-xylene. The alcohol solvent used in the present invention is a product currently sold on the market. For example, ethanol sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name of ethanol.

[0058] When the amount of the electron-rich olefin and the mixed solution is within the range, if the amount of the electron-rich olefin is less than 0.01 or greater than 0.12, the subsequent step of preparing the alternating sequence structure polymer microspheres will not be able to obtain the alternating sequence structure polymer microspheres of the present invention, and the expected alternating sequence structure polymer-based carbon microspheres cannot be obtained. The electrical properties of the carbon material as the negative electrode material of the supercapacitor are seriously affected. Therefore, the amount of the electron-rich olefin is appropriately 0.01 to 0.12, preferably 0.03 to 0.09.

[0059] When the amount of the electron-deficient olefin and the mixed solution is within the above range, if the amount of the electron-deficient olefin is less than 0.01 or greater than 0.12, the product obtained in the subsequent step of preparing the alternating sequence structure polymer microspheres is a polymer microsphere with a rough surface, and the expected alternating sequence structure polymer-based carbon microspheres cannot be obtained. Therefore, the amount of the electron-deficient olefin is appropriately 0.01 to 0.12, preferably 0.02 to 0.06.

[0060] In this step, the concentration of the mixed solution used is 60-80% by weight. If the concentration of the mixed solution is lower than 60% or higher than 80%, the alternating sequence structure polymer microspheres for preparing alternating sequence structure polymer-based carbon microspheres cannot be prepared. Therefore, the concentration of the mixed solution is suitable to be 60-80%, preferably 60-70%.

[0061] In this step, the reaction temperature is 20-70° C. If the temperature is lower than 20° C. or higher than 70° C., the charge transfer complex solution cannot be obtained. Therefore, the reaction temperature is suitably 20-70° C., preferably 20-50° C.

[0062] In this step, the stirring time is 3 to 24 hours. If the stirring time is shorter than 3 hours, the reaction will be insufficient and the charge transfer complex solution cannot be obtained; if the stirring time is longer than 24 hours, the alternating sequence structure polymer microspheres obtained subsequently will agglomerate. Therefore, the stirring time is suitable for 3 to 24 hours, preferably 3 to 18 hours.

[0063] B. Preparation of polymerization reaction solution

[0064] Adding a crosslinking agent, an initiator and a dispersant to the charge transfer complex solution obtained in step A, and performing ultrasonic dispersion to obtain a polymerization reaction solution;

[0065] The weight ratio of the crosslinking agent, initiator, dispersant and mixed solution is 0.001-0.008: 0.005-0.05: 0.002-0.02: 1;

[0066] In this step, the crosslinking agent plays a role in increasing the crosslinking density of the polymer, improving the thermal stability and the carbonization yield in the preparation of the alternating sequence structure polymer microspheres. The crosslinking agent is allyl methacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, triallyl isocyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate or vinyl trimethoxysilane, which are all products currently sold on the market, such as diallyl isophthalate sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name of diallyl isophthalate.

[0067] In this step, the role of the initiator in preparing the alternating sequence structure polymer microspheres is that it decomposes to generate free radical active species to initiate polymerization of monomers in the charge transfer complex solution. The initiator is azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide or azobiscyclohexylcarbonitrile, all of which are products currently sold on the market, such as azobisisobutyronitrile sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name of azobisisobutyronitrile.

[0068] In this step, the role of the dispersant in preparing the alternating sequence structure polymer microspheres is to stabilize the polymer particles and obtain the polymer microspheres with good monodispersity. The dispersant is polyvinyl pyrrolidone with an average molecular weight of 8000-1300000, polyacrylamide with a number average molecular weight (Mn) of 5000-18000000, polyacrylic acid with a weight average molecular weight (Mw) of 2000-5000 or 240000-250000, or polyvinyl alcohol with a weight average molecular weight (Mw) of 110000-130000 or 180000-200000, which are all products currently sold on the market, for example, Shanghai Aladdin Biochemical Technology Co., Ltd. uses the trade name of polyvinyl pyrrolidone (average molecular weight = 58000) Polyvinyl pyrrolidone (average molecular weight = 58,000) sold by Sigma-Aldrich (Shanghai) Trading Co., Ltd. under the trade name of polyacrylamide (Mn = 40,000); polyacrylic acid (Mw = 250,000) sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name of polyacrylic acid (Mw = 250,000); polyvinyl alcohol (Mn = 130,000) sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name of polyvinyl alcohol (Mn = 130,000).

[0069] In this step, the weight ratio of the crosslinking agent to the mixed solution is 0.001 to 0.008:1. If the amount of the crosslinking agent is higher than 0.008:1, the alternating sequence structure polymer microspheres obtained in the subsequent step are prone to agglomeration; if the amount of the crosslinking agent is lower than 0.001:1, the alternating sequence structure polymer microspheres obtained in the subsequent step are not sufficiently crosslinked and cannot maintain the spherical morphology during the carbonization process. Therefore, the weight ratio of the crosslinking agent to the mixed solution is 0.001 to 0.008:1, preferably 0.002 to 0.006:1.

[0070] In this step, the weight ratio of the initiator to the mixed solution is 0.005 to 0.05:1. If the amount of the initiator is higher than 0.05:1, the alternating sequence structure polymer microspheres obtained in the subsequent steps will be severely agglomerated; if the amount of the initiator is lower than 0.005:1, the alternating sequence structure polymer microspheres obtained in the subsequent steps will have uneven particle sizes. Therefore, the weight ratio of the initiator to the mixed solution is 0.005 to 0.05:1, preferably 0.006 to 0.045:1.

[0071] In this step, the weight ratio of the dispersant to the mixed solution is 0.002 to 0.02:1. If the amount of the dispersant is higher than 0.02:1, the particle size distribution of the alternating sequence structure polymer microspheres obtained in the subsequent steps is wide and the uniformity is poor; if the amount of the dispersant is lower than 0.002:1, the alternating sequence structure polymer microspheres obtained in the subsequent steps will have serious agglomeration phenomenon and spherical particles cannot be obtained. Therefore, the weight ratio of the dispersant to the mixed solution is 0.002 to 0.02:1, preferably 0.003 to 0.018:1.

[0072] C. Preparation of polymer microspheres with alternating sequence structure

[0073] The polymerization reaction liquid obtained in step B is transferred to a three-necked flask, and the polymerization reaction is carried out at a temperature of 70-80° C. and a stirring speed of 170-300 rpm for 4-6 hours. Finally, the reactant is cooled to room temperature, the product is centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 50-70° C. for 4-6 hours to obtain the alternating sequence structure polymer microspheres;

[0074] In this step, when the polymerization temperature is within the range, if the polymerization temperature is lower than 70°C, the reaction is not thorough, and the obtained alternating sequence structure polymer microspheres have low molecular weight and uneven size; if the polymerization temperature is higher than 80°C, the obtained alternating sequence structure polymer microspheres have uneven particle size. Therefore, it is reasonable for the polymerization temperature to be 70-80°C, preferably 72-75°C. When the polymerization stirring rate is within the range, if the stirring rate is lower than 170rpm, the obtained alternating sequence structure polymer microspheres are prone to crosslinking and agglomeration; if the stirring rate is higher than 300rpm, the spherical structure of the alternating sequence structure polymer microspheres is easily destroyed. Therefore, it is reasonable for the stirring rate to be 170-300rpm, preferably 170-220rpm. When the polymerization time is within the range, if the polymerization time is lower than 4h, the obtained alternating sequence structure polymer microspheres have uneven particle size; if the polymerization time is higher than 6h, the obtained alternating sequence structure polymer microspheres are prone to crosslinking. Therefore, it is reasonable for the polymerization time to be 4-6h, preferably 4-5h. When the oven temperature is within the range, if the temperature is lower than 50°C, the obtained alternating sequence structure polymer microspheres are not completely dried; if the temperature is higher than 70°C, the obtained alternating sequence structure polymer microspheres are prone to rupture. Therefore, an oven temperature of 50 to 70°C is reasonable, preferably 55 to 65°C. When the drying time is within the range, if the drying time is lower than 4h, the obtained alternating sequence structure polymer microspheres are prone to agglomeration; if the drying time is higher than 6h, the obtained alternating sequence structure polymer microspheres are prone to deformation. Therefore, a drying time of 4 to 6h is reasonable, preferably 4 to 5h.

[0075] In this step, the reactants are cooled to room temperature, centrifuged and washed with anhydrous ethanol to remove unreacted monomers and initiators. The washing step is performed until the content of unreacted monomers and initiators reaches less than 0.001% by weight.

[0076] In this step, the main purpose of drying the washed precipitate is to obtain dry alternating sequence structured polymer microspheres for preparing alternating sequence structured polymer-based carbon microspheres.

[0077] In the present invention, a scanning electron microscope sold by Japan's HITACHI Corporation under the trade name of scanning electron microscope and a transmission electron microscope sold by Japan's JEOL Corporation under the trade name of transmission electron microscope were used to observe the alternating sequence structured polymer microspheres obtained in this step, and the results showed that the alternating sequence structured polymer microspheres had a smooth surface and were uniform in size.

[0078] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0079] The alternating sequence structure polymer microspheres obtained in step C are placed in a tube furnace for pre-oxidation, dry air is introduced and heated to 250-300°C at a heating rate of 1.0-3.0°C / min, and kept warm for 1.0-2.0h; then, the pre-oxidized product is carbonized, argon is introduced for protection and heated to 600-700°C at a heating rate of 2.0-3.0°C / min, kept warm for 2.0-2.5h, and naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:1-5, and then heated to a temperature of 600-1000°C at a heating rate of 1.0-5.0°C / min under argon protection, activated at this temperature for 1.0-4.0 hours, and finally naturally cooled to room temperature, washed with deionized water to neutrality, and the alternating sequence structure polymer-based carbon microspheres can be obtained.

[0080] In this step, the purpose of pre-oxidation is to complete the cross-linking of the alternating sequence structure polymer microspheres into rings and improve the thermal stability of the material. When the pre-oxidation temperature, the holding time and the heating rate are within the range, if the heating rate is less than 1.0℃ / min, the cross-linking degree of the obtained product is insufficient; if the heating rate is higher than 3.0℃ / min, the spherical morphology of the product is easily destroyed. Therefore, a heating rate of 1.0-3.0℃ / min is reasonable; if the pre-oxidation temperature is lower than 250℃, the internal cross-linking of the obtained product is not easy to form a ring; if the pre-oxidation temperature is higher than 300℃, the spherical morphology of the product will be destroyed. Therefore, a pre-oxidation temperature of 250-300℃ is reasonable. If the holding time is shorter than 1.0h, the morphology of the obtained product is uneven; if the holding time is higher than 2.0h, the cross-linking structure inside the product is easily destroyed. Therefore, a holding time of 1.0-2.0h is reasonable.

[0081] In this step, the main function of carbonization is to improve the conductivity of carbon materials, form a stable carbon structure, and improve the thermal stability of materials. When the carbonization temperature, the holding time, and the heating rate are within the range, if the heating rate is less than 2.0°C / min, the carbonization rate of the obtained product is low; if the heating rate is higher than 3.0°C / min, the spherical morphology of the product is easily destroyed, so a heating rate of 2.0-3.0°C / min is reasonable. If the carbonization temperature is lower than 600°C, the carbonization rate of the obtained product is low; if the carbonization temperature is higher than 700°C, the morphology of the product is easily destroyed; therefore, a carbonization temperature of 600-700°C is reasonable. If the holding time is shorter than 2.0h, the carbonization degree of the obtained product is low; if the holding time is higher than 2.5h, the morphology of the obtained product is easily destroyed, so a holding time of 2.0-2.5h is reasonable.

[0082] In this step, the main function of activation is to increase the pore structure of the material and improve the specific surface area. When the heating rate, activation reaction temperature and activation time are within the range, if the ratio of the product to KOH is less than 1:1, the product activation will be incomplete, the specific surface area of ​​the carbon microspheres will be reduced, and the specific capacitance will be low; if the ratio of the product to KOH is greater than 1:5, the structure of the product will be destroyed, and carbon microspheres with complete structure and good performance cannot be obtained. Therefore, it is reasonable that the ratio of the product to KOH is 1:1 to 5. When the ratio of the product to KOH, the heating rate, the activation reaction temperature and the activation time are within the range, if the heating rate is lower than 1.0℃ / min, the degree of activation of the product is low, and less carbon material is obtained; if the heating rate is higher than 5.0℃ / min, the morphology of the product is easily destroyed; therefore, it is reasonable that the heating rate is 1.0 to 5.0℃ / min. If the activation reaction temperature is lower than 600°C, the degree of activation of the obtained carbon material is insufficient, the specific surface area is small, and the energy storage performance of the carbon material is reduced; if the activation temperature is higher than 1000°C, the pore structure of the obtained carbon material is larger, resulting in a decrease in the energy storage performance of the carbon material. Therefore, an activation reaction temperature of 600-1000°C is reasonable. If the activation reaction time is shorter than 1.0 hour, the degree of activation of the obtained carbon material is insufficient, the specific surface area is small, and the energy storage performance of the carbon material is reduced; if the activation time is longer than 4.0 hours, the porous carbon structure obtained is larger, which is not conducive to charge storage. Therefore, an activation reaction time of 1.0-4.0 hours is reasonable.

[0083] The alternating sequence structure polymer-based carbon microspheres prepared by the above-mentioned preparation method were observed using the above-mentioned scanning electron microscope and an energy spectrometer sold by Thermo Company under the trade name of energy dispersive X-ray spectrometer. The results showed that the alternating sequence structure polymer-based carbon microspheres were composed of C, N and O in a weight ratio of 70-90:6.1-19.5:3.9-10.5, and the carbon microspheres had uniform particle size, smooth surface and good dispersibility, and a specific surface area of ​​2100-3200m 2 ·g -1 between.

[0084] The present invention also relates to the alternating sequence structure polymer-based carbon microspheres, which can be used as the negative electrode material of the all-solid-state supercapacitor. The preparation method of the supercapacitor electrode material is as follows: the alternating sequence structure polymer-based carbon microspheres prepared in different batches are used as active materials and mixed with acetylene black, a binder, and N-methylpyrrolidone in a weight ratio of 7:2:1:15 to form a uniform slurry, and the slurry is evenly coated on a 1 cm 2 The working electrode was pressed onto the nickel foam after drying. In 4 mol / L KOH electrolyte, the working electrode, platinum electrode and mercury / mercury oxide electrode formed a three-electrode system. The mass specific capacitance was 1-10 A·g-1 Stable at 260~420F·g -1 When the current density is 10A·g -1 When the battery is charged and discharged for 10,000 times, the capacitance retention rate is stabilized at 95-100%.

[0085] The present invention uses an electrochemical workstation sold by Swiss Metrohm under the trade name Autolab PGSTAT302N to test cyclic voltammetry (CV), constant current charge-discharge curve (GCD) and cycle stability curve at room temperature. According to the calculation method of specific capacitance in the document "An approach to unify capacitance measurements of electric double layer capacitors using sinusoidal potential scan, Journal of Energy Storage, 66 (2023) 107522", the mass specific capacitance of the carbon material and the capacitance retention rate after 10,000 cycles are calculated, and the results are shown in the Examples section.

[0086] The present invention will be more clearly described below by the following examples, but the present invention is not limited to these examples.

[0087] The following examples use the following analysis methods to analyze the materials: scanning electron microscopy and transmission electron microscopy are used for microscopic morphology analysis, specific surface area analyzer is used to test and analyze the pore structure of alternating sequence structure polymer-based carbon microspheres, and energy dispersive X-ray spectrometer is used to test the elemental composition of the carbon material.

[0088] Embodiment 1:

[0089] A. Preparation of Charge Transfer Complex Solution

[0090] The electron-rich olefin styrene, the electron-deficient olefin maleimide and the ethanol / isoamyl acetate solution are dissolved in a mixed solution with a concentration of 60% by weight in a weight ratio of 0.02:0.03:1, wherein the weight ratio of ethanol to isoamyl acetate solution is 2.7:1, and after stirring at 30° C. for 10 hours, a charge transfer complex solution is obtained;

[0091] B. Preparation of polymerization reaction solution

[0092] Adding a crosslinking agent, diallyl phthalate, an initiator, azobisisobutyronitrile, a dispersant, polyvinyl pyrrolidone (average molecular weight = 50000), and an ethanol / isoamyl acetate solution at a weight ratio of 0.002:0.005:0.003:1 to the charge transfer complex solution obtained in step A, and uniformly dispersing by ultrasonication to obtain a polymerization reaction solution;

[0093] C. Preparation of polymer microspheres with alternating sequence structure

[0094] The polymerization reaction liquid obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out at a temperature of 72° C. and a stirring speed of 300 rpm for 6 hours. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 50° C. for 6 hours to obtain the alternating sequence structure polymer microspheres; the scanning electron microscope image thereof is shown in Figure 1 ;

[0095] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0096] The alternating sequence structure polymer microspheres obtained in step C are placed in a tubular furnace for pre-oxidation, dry air is introduced, and the temperature is increased to 250°C at a rate of 2.0°C / min, and the temperature is kept for 1.0h; then, the pre-oxidation product is carbonized, argon is introduced for protection, and the temperature is increased to 600°C at a rate of 2.0°C / min, and the temperature is kept for 2.0h, and the product is naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH in a mass ratio of 1:1, and then heated to 700°C at a rate of 2.0°C / min under argon protection, and activated at this temperature for 2.0 hours, and finally naturally cooled to room temperature, and washed with deionized water until neutral, to obtain the alternating sequence structure polymer-based carbon microspheres. See the scanning electron microscope image for its scanning electron microscope. Figure 2 .

[0097] Table 1: Energy dispersive X-ray spectrometer detection results of the alternating sequence structure polymer-based carbon microspheres based on charge transfer complex prepared in this example.

[0098] element Atomic fraction (%) Mass fraction (%) C 76.97 79.94 N 15.91 10.91 O 7.12 9.15

[0099] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 79.94:10.91:9.15. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​2207.5m 2 g.

[0100] Embodiment 2:

[0101] A. Preparation of Charge Transfer Complex Solution

[0102] The electron-rich olefin 4-cyclohexylstyrene, the electron-deficient olefin 1,2-dimaleimidoethane and the isopropanol / acetone solution were dissolved in a mixed solution with a concentration of 70% by weight in a weight ratio of 0.05:0.09:1, wherein the weight ratio of the isopropanol to the acetone solution was 2.5:1, and after stirring at 50° C. for 8 hours, a charge transfer complex solution was obtained;

[0103] B. Preparation of polymerization reaction solution

[0104] Add crosslinking agent ethylene glycol dimethacrylate, initiator dimethyl azobisisobutyrate, dispersant polyacrylamide (Mn=90000) and isopropanol / acetone solution in a weight ratio of 0.005:0.006:0.01:1 to the charge transfer complex solution obtained in step A, and obtain a polymerization reaction solution after ultrasonic dispersion;

[0105] C. Preparation of polymer microspheres with alternating sequence structure

[0106] The polymerization reaction liquid obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out for 5 hours at a temperature of 75°C and a stirring speed of 300 rpm. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 70°C for 4 hours to obtain the alternating sequence structure polymer microspheres; the scanning electron microscope image thereof is shown in Figure 3 ;

[0107] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0108] The alternating sequence structure polymer microspheres obtained in step C are placed in a tubular furnace for pre-oxidation, dry air is introduced, and the temperature is increased to 250°C at a rate of 2.0°C / min, and the temperature is kept for 1.0h; then, the pre-oxidation product is carbonized, argon is introduced for protection, and the temperature is increased to 650°C at a rate of 2.0°C / min, and the temperature is kept for 2.0h, and the product is naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:3, and then heated to 800°C at a rate of 3.0°C / min under argon protection. It is activated at this temperature for 3.0 hours, and finally naturally cooled to room temperature. It is washed with deionized water until neutral to obtain the alternating sequence structure polymer-based carbon microspheres. The scanning electron microscope image thereof is shown in Figure 4 .

[0109] Table 2: Energy dispersive X-ray spectrometer detection results of the alternating sequence structure polymer-based carbon microspheres based on charge transfer complex prepared in this example.

[0110]

[0111]

[0112] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 82.77:11.85:5.38. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​2459.1m 2 g.

[0113] Embodiment 3:

[0114] A. Preparation of Charge Transfer Complex Solution

[0115] The electron-rich olefin 1-cyclopropyl-4-vinylbenzene, the electron-deficient olefin 6,6-dimethyl-5-methylene-1,3-cyclopentadiene and ethyl acetate / n-hexane solution were dissolved in a mixed solution with a concentration of 80% by weight at a weight ratio of 0.02:0.03:1, wherein the weight ratio of ethyl acetate to n-hexane solution was 4.1:1, and after stirring at 70°C for 3 hours, a charge transfer complex solution was obtained;

[0116] B. Preparation of polymerization reaction solution

[0117] Add the crosslinking agent N,N-methylenebisacrylamide, the initiator azobiscyclohexylcarbonitrile, the dispersant polyvinyl alcohol (Mw=130000) and the ethyl acetate / n-hexane solution in a weight ratio of 0.003:0.035:0.012:1 to the charge transfer complex solution obtained in step A, and uniformly disperse by ultrasonication to obtain a polymerization reaction solution;

[0118] C. Preparation of polymer microspheres with alternating sequence structure

[0119] The polymerization reaction liquid obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out for 4 hours at a temperature of 80°C and a stirring speed of 220 rpm. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 65°C for 4.5 hours to obtain the alternating sequence structure polymer microspheres; the scanning electron microscope image thereof is shown in Figure 5 .

[0120] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0121] The alternating sequence structure polymer microspheres obtained in step C are placed in a tubular furnace for pre-oxidation, dry air is introduced, and the temperature is increased to 300°C at a heating rate of 1.0°C / min, and the temperature is kept for 2.0 hours; then, the pre-oxidation product is carbonized, argon is introduced for protection, and the temperature is increased to 700°C at a heating rate of 3.0°C / min, and the temperature is kept for 2.5 hours. Naturally cool to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:5, and then heated to a temperature of 1000°C at a heating rate of 5.0°C / min under argon protection. Activate at this temperature for 4.0 hours, and finally naturally cool to room temperature. Wash with deionized water until neutral to obtain the alternating sequence structure polymer-based carbon microspheres. See the scanning electron microscope image for its scanning electron microscope image. Figure 6 .

[0122] Table 3: Energy dispersive X-ray spectrometer test results of the alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in this example

[0123] element Atomic fraction (%) Mass fraction (%) C 88.28 85.23 N 8.25 10.54 O 3.47 4.23

[0124] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 85.23:10.54:4.23. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​2947.8m 2 g.

[0125] Embodiment 4:

[0126] A. Preparation of Charge Transfer Complex Solution

[0127] The electron-rich olefin 1-ethyl-4-vinylbenzene, the electron-deficient olefin p-nitrobenzene maleimide and the n-butanol / m-xylene solution were dissolved in a mixed solution with a concentration of 75% by weight at a weight ratio of 0.04:0.03:1, wherein the weight ratio of n-butanol to m-xylene solution was 2.58:1, and after stirring at 55°C for 7 hours, a charge transfer complex solution was obtained;

[0128] B. Preparation of polymerization reaction solution

[0129] Add crosslinking agent ethylene glycol dimethacrylate, initiator tert-butyl hydroperoxide, dispersant polyacrylamide (Mn=90000) and n-butanol / m-xylene solution in a weight ratio of 0.002:0.045:0.01:1 to the charge transfer complex solution obtained in step A, and disperse uniformly by ultrasonication to obtain a polymerization reaction solution;

[0130] C. Preparation of polymer microspheres with alternating sequence structure

[0131] The polymerization reaction solution obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out at a temperature of 70° C. and a stirring speed of 250 rpm for 6 hours. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 60° C. for 5.5 hours to obtain the alternating sequence structure polymer microspheres;

[0132] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0133] The alternating sequence structure polymer microspheres obtained in step C are placed in a tube furnace for pre-oxidation, dry air is introduced and heated to 275°C at a heating rate of 1.0°C / min, and kept warm for 2.0 hours; then, the pre-oxidized product is carbonized, argon is introduced for protection and heated to 600°C at a heating rate of 3.0°C / min, kept warm for 2.5 hours, and naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:3, and then heated to 800°C at a heating rate of 2.5°C / min under argon protection, activated at this temperature for 3.0 hours, and finally naturally cooled to room temperature, washed with deionized water until neutral, and the alternating sequence structure polymer-based carbon microspheres are obtained.

[0134] Table 4: Energy dispersive X-ray spectrometer test results of the alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in this example

[0135] element Atomic fraction (%) Mass fraction (%) C 85.26 83.71 N 8.61 11.94 O 6.13 4.35

[0136] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 83.71:11.94:4.35. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​2894.8m 2 g.

[0137] Embodiment 5:

[0138] A. Preparation of Charge Transfer Complex Solution

[0139] The electron-rich olefin 1-cyclopentyl-4-vinylbenzene, the electron-deficient olefin 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid and the methanol / acetone solution were dissolved in a mixed solution with a concentration of 60% by weight in a weight ratio of 0.03:0.07:1, wherein the weight ratio of the methanol to the acetone solution was 2.01:1, and after stirring at 60° C. for 5.5 hours, a charge transfer complex solution was obtained;

[0140] B. Preparation of polymerization reaction solution

[0141] Adding a crosslinking agent, ethylene glycol dimethacrylate, an initiator, methyl ethyl ketone peroxide, a dispersant, polyacrylic acid (Mw=200000), and a methanol / acetone solution at a weight ratio of 0.005:0.05:0.004:1 to the charge transfer complex solution obtained in step A, and uniformly dispersing by ultrasonication to obtain a polymerization reaction solution;

[0142] C. Preparation of polymer microspheres with alternating sequence structure

[0143] The polymerization reaction solution obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out at a temperature of 80° C. and a stirring speed of 270 rpm for 5 hours. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 55° C. for 5 hours to obtain the alternating sequence structure polymer microspheres;

[0144] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0145] The alternating sequence structure polymer microspheres obtained in step C are placed in a tube furnace for pre-oxidation, dry air is introduced and heated to 300°C at a heating rate of 2.0°C / min, and kept warm for 1.0h; then, the pre-oxidized product is carbonized, argon is introduced for protection and heated to 700°C at a heating rate of 2.0°C / min, kept warm for 2.5h, and naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:4, and then heated to 950°C at a heating rate of 3.5°C / min under argon protection, activated at this temperature for 3.5 hours, and finally naturally cooled to room temperature, washed with deionized water until neutral, and the alternating sequence structure polymer-based carbon microspheres are obtained.

[0146] Table 5: Energy dispersive X-ray spectrometer test results of the alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in this example

[0147] element Atomic fraction (%) Mass fraction (%) C 89.04 86.79 N 7.62 9.01 O 3.34 4.20

[0148] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 86.79:9.01:4.20. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​3007.4m 2 g.

[0149] Embodiment 6:

[0150] A. Preparation of Charge Transfer Complex Solution

[0151] The electron-rich olefin o-methylstyrene, the electron-deficient olefin p-nitrobenzene maleimide and the n-pentanol / isoamyl acetate solution are dissolved in a mixed solution with a concentration of 70% by weight in a weight ratio of 0.02:0.05:1, wherein the weight ratio of the n-pentanol to the isoamyl acetate solution is 1:1.08, and after stirring at 50° C. for 10 hours, a charge transfer complex solution is obtained;

[0152] B. Preparation of polymerization reaction solution

[0153] Adding a crosslinking agent, diallyl isophthalate, an initiator, dimethyl azobisisobutyrate, a dispersant, polyvinyl alcohol (Mw=130000), and a n-pentanol / isoamyl acetate solution in a weight ratio of 0.008:0.035:0.012:1 to the charge transfer complex solution obtained in step A, and uniformly dispersing by ultrasonication to obtain a polymerization reaction solution;

[0154] C. Preparation of polymer microspheres with alternating sequence structure

[0155] The polymerization reaction liquid obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out at a temperature of 75° C. and a stirring speed of 300 rpm for 4 hours. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 63° C. for 4.7 hours to obtain the alternating sequence structure polymer microspheres;

[0156] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0157] The alternating sequence structure polymer microspheres obtained in step C are placed in a tube furnace for pre-oxidation, dry air is introduced and heated to 250°C at a heating rate of 1.0°C / min, and kept warm for 1.0h; then, the pre-oxidized product is carbonized, argon is introduced for protection and heated to 600°C at a heating rate of 3.0°C / min, kept warm for 2.0h, and naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:1, and then heated to 700°C at a heating rate of 2°C / min under argon protection, activated at this temperature for 3.0 hours, and finally naturally cooled to room temperature, washed with deionized water until neutral, and the alternating sequence structure polymer-based carbon microspheres are obtained.

[0158] Table 6: Energy dispersive X-ray spectrometer test results of the alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in this example

[0159] element Atomic fraction (%) Mass fraction (%) C 85.37 84.92 N 9.81 10.27 O 4.82 4.81

[0160] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 84.92:10.27:4.81. It has a smooth surface and uniform size distribution on a macro scale, with a specific surface area of ​​2895.2m 2 g.

[0161] Embodiment 7:

[0162] A. Preparation of Charge Transfer Complex Solution

[0163] The electron-rich olefin 3-methoxystyrene, the electron-deficient olefin 6-maleimidocaproic acid and the isopropanol / p-xylene solution were dissolved in a mixed solution with a concentration of 60% by weight at a weight ratio of 0.04:0.07:1, wherein the weight ratio of isopropanol to p-xylene solution was 1.82:1, and after stirring at 55° C. for 12 hours, a charge transfer complex solution was obtained;

[0164] B. Preparation of polymerization reaction solution

[0165] Add a crosslinking agent N,N-methylenebisacrylamide, an initiator azobiscyclohexylcarbonitrile, a dispersant polyacrylic acid (Mw=240000) and a n-pentanol / isoamyl acetate solution in a weight ratio of 0.008:0.015:0.002:1 to the charge transfer complex solution obtained in step A, and disperse uniformly by ultrasonication to obtain a polymerization reaction solution;

[0166] C. Preparation of polymer microspheres with alternating sequence structure

[0167] The polymerization reaction solution obtained in step B was transferred to a three-necked flask, and the polymerization reaction was carried out at a temperature of 80° C. and a stirring speed of 200 rpm for 4.5 hours. Finally, the reactant was cooled to room temperature, the product was centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 68° C. for 4.3 hours to obtain the alternating sequence structure polymer microspheres;

[0168] D. Preparation of polymer-based carbon microspheres with alternating sequence structure

[0169] The alternating sequence structure polymer microspheres obtained in step C are placed in a tube furnace for pre-oxidation, dry air is introduced and heated to 275°C at a heating rate of 1.5°C / min, and kept warm for 2.0 hours; then, the pre-oxidized product is carbonized, argon is introduced for protection and heated to 650°C at a heating rate of 3.0°C / min, kept warm for 2.5 hours, and naturally cooled to room temperature to obtain a black solid. The obtained black product is mixed with KOH at a mass ratio of 1:3, and then heated to 950°C at a heating rate of 2°C / min under argon protection, activated at this temperature for 3.0 hours, and finally naturally cooled to room temperature, washed with deionized water until neutral, and the alternating sequence structure polymer-based carbon microspheres are obtained.

[0170] Table 7: Energy dispersive X-ray spectrometer test results of the alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in this example

[0171] element Atomic fraction (%) Mass fraction (%) C 86.07 85.94 N 8.29 8.64 O 5.64 5.42

[0172] According to the test results of the scanning electron microscope and the energy dispersive X-ray spectrometer, the alternating sequence structure polymer-based carbon microspheres prepared in this embodiment are composed of C, N and O elements in a weight ratio of 85.94:8.64:5.42. It has a smooth surface and is evenly dispersed in size. The specific surface area is 2917.2m 2 g.

[0173] The electron-rich olefins, electron-deficient olefins, mixed solutions, crosslinking agents, initiators, and dispersants used in the above embodiments may also be other types of substances within the aforementioned limited range, all of which can achieve similar technical effects as embodiments 1-7, and will not be illustrated one by one here.

[0174] Application Example 1:

[0175] The implementation method of this application example is as follows:

[0176] The alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in Example 1 were mixed with acetylene black, a binder, and N-methylpyrrolidone in a weight ratio of 7:2:1:15 to form a uniform slurry, and evenly coated on a 1 cm 2 The working electrode was pressed onto the nickel foam and dried. The working electrode, mercury / mercury oxide electrode and 4 mol / L KOH electrolyte formed a three-electrode system. The CV, GCD and cycle stability curves were tested at room temperature using an electrochemical workstation sold by Swiss Metrohm under the trade name Autolab PGSTAT 302N. The mass specific capacitance and cycle stability of the alternating sequence structure polymer-based carbon microspheres were calculated according to the method described in this specification. The results are listed in the attached figure. Figure 7 . Figure 7 It can be seen that the material has a current density of 1A·g -1 , 2A·g -1 , 5A g -1 , 10A·g -1 The mass specific capacitance is 364.4F·g -1 、321.8F·g -1 、303.1F·g -1 , 285.6F·g -1 When the current density is 10A·g -1 The capacitance retention rate after 10,000 charge and discharge cycles was 98%. The alternating sequence structure polymer-based carbon microspheres prepared by the same preparation method and different batches were -1 The mass specific capacitance is stable at 300~380F·g -1 between.

[0177] Application Example 2:

[0178] The implementation method of this application example is as follows:

[0179] The alternating sequence structure polymer-based carbon microspheres based on the charge transfer complex prepared in Example 2 were mixed with acetylene black, a binder, and N-methylpyrrolidone in a weight ratio of 7:2:1:15 to form a uniform slurry, and evenly coated on a 1 cm 2 The working electrode was pressed onto the nickel foam and dried. The working electrode, mercury / mercury oxide electrode and 4 mol / L KOH electrolyte formed a three-electrode system. The CV, GCD and cycle stability curves were tested at room temperature using an electrochemical workstation sold by Swiss Metrohm under the trade name Autolab PGSTAT 302N. The mass specific capacitance and cycle stability of the alternating sequence structure polymer-based carbon microspheres were calculated according to the method described in this specification. The results are listed in the attached figure. Figure 8 . Figure 8 It can be seen that the material has a current density of 1A·g -1 , 2A·g -1 , 5A g -1 , 10A·g -1 The mass specific capacitance is 341.3F·g -1 、317.5F·g -1 、293.9F·g -1 、269.4F·g -1 When the current density is 10A·g -1 The capacitance retention rate after 10,000 charge and discharge cycles was 96%. The alternating sequence structure polymer-based carbon microspheres prepared by the same preparation method and different batches were -1The mass specific capacitance is stable at 280~370F·g -1 between.

[0180] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. An alternating sequence structure polymer-based carbon microsphere, characterized in that: The alternating sequence structure polymer-based carbon microspheres are prepared by using alternating sequence structure polymer microspheres as carbon precursors through pyrolysis and carbonization activation steps; The alternating sequence structure polymer microspheres are polymer microspheres with an alternating polymer chain structure formed by using a charge transfer complex formed by an electron-rich olefin and an electron-deficient olefin as a polymerization monomer through free radical polymerization.

2. The alternating sequence structure polymer-based carbon microspheres according to claim 1, characterized in that: The electron-rich olefin is a styrene monomer, or a styrene monomer substituted with a hydroxyl group, an amino group, an alkyl group, an alkoxy group, an aryloxy group, a boric acid group or an amide group.

3. The alternating sequence structure polymer-based carbon microspheres according to claim 2, characterized in that: The electron-rich olefin is styrene, p-hydroxystyrene, 4-vinylaniline, 2-aminostyrene, 4-vinylbenzene boronic acid, 4-vinylbenzenesulfonamide, 3-methoxystyrene, 4-methoxystyrene, 2,4-dimethoxy-1-vinylbenzene, p-phenoxystyrene, o-methylstyrene, 3-methoxystyrene, 4-methylstyrene, α-methylstyrene, 4-isopropylstyrene, 4-cyclohexylstyrene, 4-tert-butylstyrene, 1-ethyl-4-vinylbenzene, 1-cyclopropyl-4-vinylbenzene or 1-cyclopentyl-4-vinylbenzene.

4. The alternating sequence structure polymer-based carbon microspheres according to claim 1, characterized in that: The electron-deficient olefin is a maleimide monomer, or a maleimide monomer substituted with a halogen atom, an amino group, a hydroxyl group, an amide group, a carboxyl group, an aromatic group or an alkyl group, or 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene.

5. The alternating sequence structure polymer-based carbon microspheres according to claim 4, characterized in that: The electron-deficient olefin is maleimide, N-methylmaleimide, N-bromomaleimide, N-aminomaleimide, N-phenylmaleimide, N-benzylmaleimide, p-nitrobenzenemaleimide, N-carbamylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-n-butylmaleimide, N-tert-butylmaleimide, N-(1-pyrene)-maleimide, 4-maleimidophenol, N-hydroxymaleimide, 2-maleimidoacetic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 5-hydroxy-maleimide, -maleimidovaleric acid, 6-maleimidohexanoic acid, 4-maleimidobenzoic acid, N,N'-1,4-phenylenedimaleimide, N-hydroxyethylmaleimide, 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 9-maleimidoacridine, 1-cyclopentylpyrrole-2,5-dione, 1-(1-naphthyl)-1H-pyrrole-2,5-dione, 1,2-bismaleimidoethane, 1,4-bis(maleimido)butane, 1,6-bismaleimidohexane or 6,6-dimethyl-5-methylene-1,3-cyclopentadiene.

6. The alternating sequence structure polymer-based carbon microspheres according to claim 1, characterized in that: The alternating sequence structure polymer-based carbon microspheres are composed of C, N and O in a weight ratio of 70 to 90: 6.1~19.5:3.9~10.5, the carbon ball has uniform particle size, smooth surface and good dispersion, and the specific surface area is 2100~3200m 2 ·g -1 between.

7. A method for preparing alternating sequence structure polymer-based carbon microspheres according to any one of claims 1 to 6, characterized in that: The following steps are involved: A. Preparation of Charge Transfer Complex Solution The electron-rich olefin and the electron-deficient olefin are dissolved in a mixed solution with a concentration of 60 to 80% by weight, and stirred for reaction at a temperature of 20 to 70° C. for 3 to 24 hours to obtain a charge transfer complex solution; B. Preparation of polymerization reaction solution Adding a crosslinking agent, an initiator and a dispersant to the charge transfer complex solution obtained in step A, and performing ultrasonic dispersion to obtain a polymerization reaction solution; C. Preparation of polymer microspheres with alternating sequence structure The polymerization reaction solution obtained in step B is transferred to a three-necked flask, and the polymerization reaction is carried out at a temperature of 70-80° C. and a stirring speed of 170-300 rpm for 4-6 hours. Finally, the reactant is cooled to room temperature, the product is centrifuged and washed with anhydrous ethanol to completely remove the unreacted monomer and initiator, and then placed in an oven and dried at a temperature of 50-70° C. for 4-6 hours to obtain alternating sequence structure polymer microspheres; D. Preparation of polymer-based carbon microspheres with alternating sequence structure The alternating sequence structure polymer microspheres obtained in step C are placed in a tubular furnace for pre-oxidation, dry air is introduced, and the mixture is heated to 250-300°C at a heating rate of 1.0-3.0°C / min, and kept warm for 1.0-2.0h; then, the pre-oxidized product is carbonized, argon is introduced for protection, and the mixture is heated to 600-700°C at a heating rate of 2.0-3.0°C / min, and kept warm for 2.0-2.5h, and naturally cooled to room temperature to obtain a black solid; the obtained black product is mixed with KOH in a mass ratio of 1:1-5, and then heated to a temperature of 600-1000°C at a heating rate of 1.0-5.0°C / min under argon protection, and activated at this temperature for 1.0-4.0 hours, and finally naturally cooled to room temperature, and washed with deionized water until neutral, to obtain the alternating sequence structure polymer-based carbon microspheres.

8. The method for preparing alternating sequence structure polymer-based carbon microspheres according to claim 7, characterized in that: In step A, the weight ratio of the electron-rich olefin, the electron-deficient olefin and the mixed solution is 0.01-0.12:0.01-0.12:1; In step B, the weight ratio of the crosslinking agent, initiator, dispersant and mixed solution is 0.001-0.008:0.005-0.05:0.002-0.02:

1.

9. The method for preparing alternating sequence structure polymer-based carbon microspheres according to claim 7, characterized in that: In step A, the mixed solution is selected from a mixed solution of any two of methanol, ethanol, propanol, butanol, isopropanol, n-butanol, n-pentanol, isoamyl alcohol, acetone, ethyl acetate, isoamyl acetate, n-hexane, cyclohexane, m-xylene, and p-xylene; In step B: The crosslinking agent is allyl methacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ethylene glycol dimethacrylate, N,N-methylenebisacrylamide, triallyl isocyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate or vinyl trimethoxysilane; The initiator is azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide or azobiscyclohexylcarbonitrile; The dispersant is polyvinyl pyrrolidone with an average molecular weight of 8000-1300000, polyacrylamide with a number average molecular weight of 5000-18000000, polyacrylic acid with a weight average molecular weight of 2000-5000 or 240000-250000, or polyvinyl alcohol with a weight average molecular weight of 110000-130000 or 180000-200000.

10. Use of the alternating sequence structure polymer-based carbon microspheres according to any one of claims 1 to 6 as a negative electrode material for an all-solid-state supercapacitor.

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